sulfur resistance of bi-metallic Ni catalysts

双金属Ni催化剂的抗硫性能

• 批准号: 323201401
• 负责人: Privatdozent Dr.-Ing. Martin Seipenbusch
• 金额: --
• 依托单位: ParteQ GmbH
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2020-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/323201401?language=en
• 关键词: sulfur; resistance; bi; metallic; Ni

The loss of catalytic activity due to poisoning of metallic surfaces with sulfur is problematic in many areas of application. Examples for this are the conversion of biomass into liquid fuels and chemicals, the catalytic reduction of higher polyaromatics in diesel fuel and the operation of solid oxide fuel cells. An increase of the sulfur resistance of heterogeneous catalysts is therefore of great interest.The aim of the proposed project is the testing of the hypothesis according to which a change in the electronic band structure of a metal catalyst can lead to an increase in sulfur resistance. This shall be accomplished by alloying a base metal with two other components. Literature search yielded two Ni-alloys of particular interest, which will be investigated as model system. For one this is Ni-Ru, for which a change in the density of states at the Fermi-level and at the same time an alteration of S-adsorption were theoretically shown. The second system is Ni-Sb, for which a strong increase in S-resistance was experimentally shown but no mechanistic explanation could be found. For both systems the effect of sulfur on the catalytic properties and the mechanisms of deactivation shall be studied making use of online characterization methods and the excellent possibilities for particle structuring offered by aerosol systems.From the definition of the project goals three core questions result:How does the adsorption of sulfur depend on the composition of alloyed particles?How does the electronic structure of alloyed metal particles change with composition?How does the catalytic activity of a test reaction change with time in the presence of sulfur and as a function of particle composition?The experimental procedure can be organized in three steps. The first step will comprise the generation of binary alloyed particles of controlled size and composition, which will be carefully characterized. For the latter online aerosol methods but additionally offline tools will be employed. A core online tool will be aerosol photoemission spectrometry (APES), which allows the characterization of the electronic structure of the particles. In a second step sulfur adsorption on the particle surfaces will be investigated, also relying in part on APES. The third step will focus on the investigation of the catalytic activity of the structures and their sulfur resistance in dependence on particle composition.

由于金属表面被硫毒化而导致的催化活性的损失在许多应用领域中是有问题的。这方面的例子是将生物质转化为液体燃料和化学品，催化还原柴油燃料中的高级多环芳烃，以及固体氧化物燃料电池的运行。因此，提高非均相催化剂的抗硫性是一个非常重要的课题。本课题的目的是验证金属催化剂电子能带结构的变化可以提高抗硫性的假设。这应通过将一种基底金属与两种其他成分合金化来实现。文献检索产生了两种特别感兴趣的镍合金，将作为模型系统进行研究。其中之一是Ni-Ru，理论上显示出费米能级的态密度发生变化，同时S吸附发生变化。第二个系统是Ni-Sb系统，实验表明其抗硫性大大增加，但找不到机理解释。对于这两个系统，应利用在线表征方法和气溶胶系统提供的颗粒结构化的极好可能性，研究硫对催化性能的影响和失活机理。从项目目标的定义中得出三个核心问题：硫的吸附如何取决于合金颗粒的组成？合金化金属颗粒的电子结构如何随成分变化？在存在硫的情况下，测试反应的催化活性如何随时间变化以及作为颗粒组成的函数？实验过程可以分为三个步骤。第一步将包括控制尺寸和组成的二元合金颗粒的生成，其将被仔细表征。对于后者，将采用在线气溶胶方法，但另外采用离线工具。核心在线工具将是气溶胶光发射光谱法（APES），它可以表征颗粒的电子结构。在第二步中，将研究颗粒表面上的硫吸附，也部分依赖于APES。第三步将集中于研究结构的催化活性和它们依赖于颗粒组成的抗硫性。